CN109437225A - A kind of synthetic method and device of silica-rich zeolite molecular sieve - Google Patents
A kind of synthetic method and device of silica-rich zeolite molecular sieve Download PDFInfo
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- CN109437225A CN109437225A CN201811487766.1A CN201811487766A CN109437225A CN 109437225 A CN109437225 A CN 109437225A CN 201811487766 A CN201811487766 A CN 201811487766A CN 109437225 A CN109437225 A CN 109437225A
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 89
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000010457 zeolite Substances 0.000 title claims abstract description 89
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 54
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 48
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000010189 synthetic method Methods 0.000 title claims abstract description 28
- 239000000376 reactant Substances 0.000 claims abstract description 79
- 238000001816 cooling Methods 0.000 claims abstract description 40
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 22
- 239000010703 silicon Substances 0.000 claims abstract description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims description 66
- 239000000463 material Substances 0.000 claims description 27
- 229910001868 water Inorganic materials 0.000 claims description 24
- 230000007246 mechanism Effects 0.000 claims description 20
- 229910052681 coesite Inorganic materials 0.000 claims description 13
- 229910052906 cristobalite Inorganic materials 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 13
- 229910052682 stishovite Inorganic materials 0.000 claims description 13
- 238000003786 synthesis reaction Methods 0.000 claims description 13
- 229910052905 tridymite Inorganic materials 0.000 claims description 13
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 229910052593 corundum Inorganic materials 0.000 claims description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 10
- 235000019353 potassium silicate Nutrition 0.000 claims description 9
- 239000011541 reaction mixture Substances 0.000 claims description 9
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 9
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical group [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 8
- 238000005342 ion exchange Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 2
- 230000004044 response Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 24
- 230000008569 process Effects 0.000 abstract description 10
- 238000007599 discharging Methods 0.000 abstract description 5
- 230000008859 change Effects 0.000 abstract description 4
- 238000012805 post-processing Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000007787 solid Substances 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 5
- 238000007664 blowing Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- URLKBWYHVLBVBO-UHFFFAOYSA-N p-dimethylbenzene Natural products CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- -1 paraxylene toluene Chemical compound 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 241000446313 Lamella Species 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- QCWMRAKRSCVYNJ-UHFFFAOYSA-N methanol;prop-1-ene Chemical group OC.CC=C QCWMRAKRSCVYNJ-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
Abstract
The present invention provides the synthetic methods and device of a kind of silica-rich zeolite molecular sieve.This method comprises: reactant is prepared: the reactant for taking suitable silicon source, silicon source, template, sulfuric acid and deionized water to carry out default proportion is prepared；Zeolite product is produced: reactant being placed in synthesizer and carries out hydro-thermal reaction, when temperature rises to preset hydrothermal temperature, the volatilizable component for discharging predetermined amount in reactant outward by synthesizer, makes the proportion of reactant change, to form the zeolite product of predetermined pattern；Molecular sieve is produced: obtaining zeolite molecular sieve to the cooling post-processing of zeolite product.In the present invention, method by discharging volatilizable organic or inorganic component in reactant outward during hydro-thermal reaction carries out, the proportion of hydrothermal reaction process and middle reactant is controlledly changed, and then ensure that and can synthesize the various zeolite products with different-shape under conditions of not changing reactant original proportion.
Description
Technical field
The present invention relates to technical field of chemical synthesis, in particular to a kind of synthetic method of silica-rich zeolite molecular sieve
And device.
Background technique
Currently, the shape-selective separation of zeolite molecular sieve and catalytic performance are that it is wide with sciemtifec and technical sphere in industry relevant to chemistry
The most important properties of general application.For a certain catalytic reaction process, usually only the zeolite of 1-2 kind specific structure type is suitble to
As industrial catalyst.The study found that the reaction selectivity of catalyst and the crystal morphology of selected zeolite are closely related.Example
As laminar ZSM-5 in the catalysis reaction of preparing olefin by methyl alcohol dewatering diene (ethylene and propylene) yield up to 60%, propylene/
Ethylene ratio 8.4 (chemistry of fuel journal 2015 43 (6), P747-753).For another example closed in the reaction mixture for being added to ethyl alcohol
At hexagonal plate ZSM-5 zeolite, in the reaction of toluene and methanol alkylation paraxylene toluene conversion improve 5-
8%, Selectivity for paraxylene improves 1-2% (petroleum journal (PETROLEUM PROCESSING) 2017 33 (4), P654-661).Chinese patent
(application number 201711296662.8) proposes, in the liquid-phase catalysis conversion reaction of benzyl alcohol and trimethylbenzene, diplopore lamella ZSM-5
The conversion ratio of the reaction of catalyst alkylation made of zeolite reaches 98.43%.
Meanwhile for a certain zeolite, synthetic method is different, and often the pattern of product is also not quite similar.At present it is known that
Synthetic method, which sums up just, hydrothermal synthesis method, solvent-thermal process method, gas phase synthesis method, dry glue gel method, ion thermal synthesis
Method and microwave process for synthesizing etc..In addition, there are also a kind of extremely dense system synthetic method, it is living using solid silicon source and organic composite surface
Property agent be raw material, can fabricated in situ special appearance ZSM-5 molecular sieve, have good isomerization performance (petroleum refining and stone
Oiling work 2010VoL 41, No.1, P40-46).In these synthetic methods, only hydrothermal synthesis method is most mature, using most
Universal industrial preparative method.In this method, prepare sol form reactant silicon raw material be usually water content cheap and easy to get very
High waterglass or silica solution.Therefore, with these silicon raw materials come when preparing synthesis reaction mixture, water/silica mole
Than generally cannot be below 15.If it is desired to these silicon sources be formulated for dry glue synthesis or vapour/solid state reaction kinetics used in reaction
Mixture, just must first be made the higher colloidal sol of water content or gel, and reheating evaporates wherein extra moisture content, is made and is free of
Water or the low reaction mixture of water content.
Numerous studies discovery, influence product morphology because being known as synthetic method, synthesis material (silicon source and silicon source) organic is led
To the type and dosage of agent, the addition of surfactant, reactant ratio, reaction temperature and time etc..
In above-mentioned technical proposal, in all synthetic methods, once reaction mixture is prepared by the proportion calculated, water
Thermal response temperature and time is determining and starts to carry out, and the pattern of product Zeolite, which just has determined, to be changed.
Summary of the invention
In consideration of it, the invention proposes the synthetic methods and device of a kind of silica-rich zeolite molecular sieve, it is intended to solve existing height
Once reaction mixture is prepared by the proportion calculated in silicone zeolite sieve synthesis procedure, hydrothermal temperature and time
It determines and starts to carry out, the pattern of product Zeolite just has determined the problem of can not changing.
On one side, the invention proposes a kind of synthetic method of silica-rich zeolite molecular sieve, include the following steps:
Reactant is prepared: taking suitable silicon source, silicon source, template, sulfuric acid and deionized water to carry out according to default step pre-
The reactant of establishing ratio is prepared；
Zeolite product is produced: the reactant is placed in synthesizer and carries out hydro-thermal reaction, when temperature rise to it is default
Hydrothermal temperature when, discharge the volatilizable component of predetermined amount in reactant outward by the synthesizer, make the conjunction
It changes at the proportion of reactant in device, to form the zeolite product of predetermined pattern；
Molecular sieve is produced: the slurry containing the zeolite product is taken out after the synthesizer is cooling, through filtering, washing,
Roasting and ion-exchange treatment, obtain zeolite molecular sieve.
Further, in the synthetic method of above-mentioned silica-rich zeolite molecular sieve, the predetermined amount of the volatile component passes through
The synthesizer discharges the time of volatile material outward to determine.
Further, in the synthetic method of above-mentioned silica-rich zeolite molecular sieve, the silicon source be waterglass and/or silica solution,
Source of aluminium is aluminum sulfate, the tetrapropylammonium hydroxide that the template is.
Further, in the synthetic method of above-mentioned silica-rich zeolite molecular sieve, the default proportion of the reactant is Na2O:
TPA2O:SiO2:Al2O3:H20=1.5:1.0:400:1.0:25.
Further, in the synthetic method of above-mentioned silica-rich zeolite molecular sieve, the temperature of the hydro-thermal reaction is 170 DEG C.
Further, in the synthetic method of above-mentioned silica-rich zeolite molecular sieve, the time of the hydro-thermal reaction is that 12-48 is small
When.
Further, in the synthetic method of above-mentioned silica-rich zeolite molecular sieve, the predetermined pattern of the zeolite product is square
Shape, rice-shaped, thin stick-like or honeycomb.
Compared with prior art, the beneficial effects of the present invention are the synthesis of silica-rich zeolite molecular sieve provided by the invention
Method, the method by discharging volatilizable organic or inorganic component in reactant outward during hydro-thermal reaction carries out, has
The proportion of hydrothermal reaction process and middle reactant is changed to control, and then ensure that in the item for not changing the original proportion of reactant
The various zeolite products with different-shape can be synthesized under part.
Especially, the synthetic method of silica-rich zeolite molecular sieve of the invention, by being released outward in control hydrothermal reaction process
The time of volatile material is put to control the burst size of volatile material, to change the proportion of reactant, is effectively reduced
Operation difficulty in reaction process, greatly facilitates the later period calculating matched practical to reactant.
On the other hand, the invention also provides a kind of synthesizers of silica-rich zeolite molecular sieve, comprising:
Reaction kettle；
Mechanism for opening/closing is arranged on the reaction kettle, opens when the temperature of reaction kettle rises to preset reaction temperature
The volatilizable component in the reaction mixture of predetermined amount is opened and discharges outward, so that the proportion of reactant is sent out in the reaction kettle
It is raw to change；
Cooling body is connected with the mechanism for opening/closing, passes through the mechanism for opening/closing in reaction process from institute for cooling down
The volatile material released in reaction kettle is stated, in order to be collected to the volatile material after cooling；
Collector is connected with the cooling body, for collecting the volatile object cooling through the cooling body
Matter.
Further, in the synthesizer of above-mentioned silica-rich zeolite molecular sieve, the mechanism for opening/closing includes:
It can pressure-releasing type high pressure valve for discharge volatizable material in the reaction kettle.
Further, in the synthesizer of above-mentioned silica-rich zeolite molecular sieve, the cooling body includes:
Cooling coil for the cooling volatizable material released through the mechanism for opening/closing.
Compared with prior art, the beneficial effects of the present invention are the synthesis of silica-rich zeolite molecular sieve provided by the invention
Device discharges the volatilizable component of predetermined amount in reactant by synthesizer, in turn outward in hydrothermal reaction process
So that the proportion of reactant changes in synthesizer, it is effectively guaranteed under conditions of not changing reactant original proportion
The various zeolite products with different default patterns can be synthesized.
Especially, the synthesizer of silica-rich zeolite molecular sieve of the invention, by the way that mechanism for opening/closing is arranged on reaction kettle, with
Convenient for opening the mechanism for opening/closing when temperature of reaction kettle rises to scheduled reaction temperature for discharging in a certain amount of reactant
Volatizable material effectively ensured volatilizable with changing the proportion of reactant in reaction kettle during hydro-thermal reaction carries out
Controllability of property substance during release, greatly facilitates the later period calculating matched practical to reactant.
Further, the present invention is facilitating collection to release through mechanism for opening/closing by setting cooling body and collector
While volatile material, it is practical to reactant the volatile material that the later period is collected into according to collector has been further facilitated
The calculating of proportion, and then effectively ensure the accuracy of calculating.
Detailed description of the invention
By reading the following detailed description of the preferred embodiment, various other advantages and benefits are common for this field
Technical staff will become clear.The drawings are only for the purpose of illustrating a preferred embodiment, and is not considered as to the present invention
Limitation.And throughout the drawings, the same reference numbers will be used to refer to the same parts.In the accompanying drawings:
Fig. 1 is the flow chart of the synthetic method of silica-rich zeolite molecular sieve provided in an embodiment of the present invention；
Fig. 2 is the structure chart of the synthesizer of silica-rich zeolite molecular sieve provided in an embodiment of the present invention；
Fig. 2 is the structure chart of the synthesizer of silica-rich zeolite molecular sieve provided in an embodiment of the present invention；
Fig. 3 is the XRD diffraction spectrogram for the silica-rich zeolite molecular sieve powder that the embodiment of the present invention one to four provides；
Fig. 4 is the SEM scanning figure for the silica-rich zeolite molecular sieve powder that the embodiment of the present invention one to four provides.
Specific embodiment
The preferred embodiment of the present invention described with reference to the accompanying drawings.It will be apparent to a skilled person that this
A little embodiments are used only for explaining technical principle of the invention, it is not intended that limit the scope of the invention.
It should be noted that in the description of the present invention, the instruction such as term " on ", "lower", "left", "right", "inner", "outside"
Direction or the term of positional relationship be direction based on the figure or positional relationship, this is intended merely to facilitate description, and
It is not that indication or suggestion described device or element must have a particular orientation, be constructed and operated in a specific orientation, therefore not
It can be interpreted as limitation of the present invention.
In addition it is also necessary to explanation, in the description of the present invention unless specifically defined or limited otherwise, term " peace
Dress ", " connected ", " connection " shall be understood in a broad sense, for example, it may be being fixedly connected, may be a detachable connection, or integrally
Connection；It can be mechanical connection, be also possible to be electrically connected；Can be directly connected, can also indirectly connected through an intermediary,
It can be the connection inside two elements.To those skilled in the art, it can understand that above-mentioned term exists as the case may be
Concrete meaning in the present invention.
As shown in fig.1, being the synthetic method of silica-rich zeolite molecular sieve provided in an embodiment of the present invention comprising:
Reactant is prepared: taking suitable silicon source, silicon source, template, sulfuric acid and deionized water to carry out according to default step pre-
The reactant of establishing ratio is prepared.Wherein, silicon source is industrial waterglass (Na2O-7.5%；SiO2- 28%) or silica solution；Silicon source is
Aluminum sulfate；Template is tetrapropylammonium hydroxide (TPAOH) aqueous solution, the content of preferred tetrapropylammonium hydroxide (TPAOH)
It is 20%；PH value is adjusted with the industrial concentrated sulfuric acid.
Specifically, weighing aluminum sulfate solid first is dissolved in composition A liquid in the diluted concentrated sulfuric acid of deionized water；Then it weighs
Solid sodium hydroxide is added to TPAOH solution and is mixed into B liquid；The B liquid is poured slowly into the A liquid again, generation is coagulated
Glue stirs 2 hours strongly, it is made to be uniformly mixed the reactant in the default proportion of approximate sol form.Preferably, each group in reactant
The default proportion divided is Na2O:TPA2O:SiO2:Al2O3:H20=1.5:1.0:400:1.0:25.
Zeolite product is produced: the reactant is placed in synthesizer and carries out hydro-thermal reaction, when temperature rise to it is default
Hydrothermal temperature when, discharge the volatilizable component of predetermined amount in reactant outward by the synthesizer, make the conjunction
It changes at the proportion of reactant in device, to form the zeolite product of predetermined pattern.
Specifically, described be added in synthesizer according to the default reactant being formulated is subjected to hydro-thermal reaction,
When the temperature in synthesizer to rise 170 DEG C when, by the synthesizer outward within a certain period of time discharge reactant in
Volatilizable component then carries out hydro-thermal reaction 12-48 hours so that the proportion of reactant changes in the synthesizer,
To form the zeolite product of predetermined pattern.Wherein, the predetermined pattern of the zeolite product be square block, rice-shaped, it is thin stick-like or
Honeycomb.
Molecular sieve is produced: the slurry containing the zeolite product is taken out after the synthesizer is cooling, through filtering, washing,
The processing such as roasting and ion-exchange treatment, obtains zeolite molecular sieve.
Specifically, opening device to be synthesized after cooling after hydro-thermal reaction, the slurry of the zeolite containing synthetic product is taken out,
Mother liquor in filtering removal slurry, solid matter with deionized water is dried after being washed till PH=6-8 in 120 DEG C, then is placed in 600 DEG C
Blowing air roasts 6-8 hours in muffle furnace, and the product after the organic matter TPA in product is burnt out is cooling, solid with 0.5N hydrochloric acid, liquid
It is exchanged 2 hours, totally 3 times than 10 to 1,90 DEG C.After ion exchange, filtration washing to PH=3-5, drying, 550 DEG C of roastings
2h obtains zeolite molecular sieve.
As shown in fig.2, being the synthesizer of silica-rich zeolite molecular sieve provided in an embodiment of the present invention comprising: reaction
Kettle 1, mechanism for opening/closing 2, cooling body 3 and collector 4.In use process, when the temperature in reaction kettle 1 rises to preset temperature
Make, opens mechanism for opening/closing 2 for the volatizable material in reaction kettle 1 and discharge predetermined amount outward, and then is original not changing reactant
The zeolite product of different-shape can be synthesized in the case where proportion according to the actual situation.
Specifically, reaction kettle 1, is a housing member, carries out the reaction of hydro-thermal reaction in use process as reactant
Place, with ensure hydro-thermal reaction can according to preset condition (such as: default reaction temperature, default reaction time etc.) smoothly into
Row, and then content and the concentration etc. that ensure various substances in reaction process can be controlled effectively, and finally ensure
Product can satisfy various demands.
Specifically, mechanism for opening/closing 2, be one can pressure-releasing type high pressure valve, be arranged 1 on the reaction kettle, reacting
Cheng Zhong passes through the time of the control unlatching of mechanism for opening/closing 2 when the temperature in the reaction kettle 1 rises to preset reaction temperature
It is discharged into the volatile material in reaction kettle 1 in reactant outside the reaction kettle 1 according to predetermined amount, so that the reaction kettle
The proportion of reactant changes in 1, and then the zeolite product of different-shape is formed in hydro-thermal reaction.Certainly, mechanism for opening/closing 2
It can also be other components, as long as can discharge in hydrothermal reaction process convenient for reaction kettle 1 can send out substance i.e. inside it
It can.
Specifically, cooling body 3, is a cooling coil, and be connected by connecting tube 5 with the mechanism for opening/closing 2, uses
The volatile material released from the reaction kettle 1 in cooling reaction process by the mechanism for opening/closing 2, so as to
It is collected in the volatile material after cooling.
Specifically, collector 4, is connected by connecting tube 2 with the cooling body 3, for collecting from reaction kettle 1
The volatile material for being cooled to liquid through the cooling body 2 is released, is existed to calculate the reactant in reaction kettle 1
Carry out practical proportion when hydro-thermal reaction.
It below will invention is further explained further combined with specific embodiment.
Embodiment one:
Firstly, by the default proportion Na of reactant2O:TPA2O:SiO2:Al2O3:H20=1.5:1.0:400:1.0:25 is weighed
The synthesis materials such as quantitative silicon raw material waterglass, aluminum feedstock aluminum sulfate, template TPAOH solution, sulfuric acid and deionized water carry out
Reactant is prepared；Then, prepared reactant is poured into reaction kettle, volume compactedness 80%, and the reaction kettle is heated
To 170 DEG C, hydro-thermal reaction 48h；Finally, to the cooling slurry for taking out the zeolite containing synthetic product of reaction kettle, in filtering removal slurry
Mother liquor, solid matter with deionized water is washed till after PH=6-8 dries in 120 DEG C, then is placed in blowing air in 600 DEG C of muffle furnace
Roasting 6-8 hours, the product after the organic matter TPA in product is burnt out is cooling, with 0.5N hydrochloric acid, liquid-solid ratio 10 to 1,90 DEG C of friendships
It changes 2 hours, totally 3 times.After ion exchange, filtration washing to PH=3-5, drying, 550 DEG C of roasting 2h are to get to square block
Zeolite.
Embodiment two:
Firstly, by the default proportion Na of reactant2O:TPA2O:SiO2:Al2O3:H20=1.5:1.0:400:1.0:25 is weighed
The synthesis materials such as quantitative silicon raw material waterglass, aluminum feedstock aluminum sulfate, template TPAOH solution, sulfuric acid and deionized water carry out
Reactant is prepared；Then, prepared reactant is poured into reaction kettle, volume compactedness 80%, and the reaction kettle is heated
To 170 DEG C, this valve, hydro-thermal reaction 36h are turned off after opening high pressure valve release 2 minutes immediately；Finally, being taken to reaction kettle cooling
The slurry of the zeolite containing synthetic product out, the mother liquor in filtering removal slurry, solid matter with deionized water be washed till after PH=6-8 in
120 DEG C of drying, then be placed in blowing air in 600 DEG C of muffle furnace and roast 6-8 hours, after the organic matter TPA in product is burnt out
Product is cooling, is exchanged 2 hours, totally 3 times with 0.5N hydrochloric acid, liquid-solid ratio 10 to 1,90 DEG C.After ion exchange, filtration washing is extremely
PH=3-5, drying, 550 DEG C of roasting 2h are to get the zeolite for arriving rice-shaped.It can in the reactant collected in collector at this point, weighing
The weight of volatile ingredient water, the proportion for calculating the reactant in kettle at this time is Na2O:TPA2O:SiO2:Al2O3:H20=1.5:
1.0:400:1.0:19。
Embodiment three:
Firstly, by the default proportion Na of reactant2O:TPA2O:SiO2:Al2O3:H20=1.5:1.0:400:1.0:25 is weighed
The synthesis materials such as quantitative silicon raw material waterglass, aluminum feedstock aluminum sulfate, template TPAOH solution, sulfuric acid and deionized water carry out
Reactant is prepared；Then, prepared reactant is poured into reaction kettle, volume compactedness 80%, and the reaction kettle is heated
To 170 DEG C, this valve is turned off after opening high pressure valve release 4 minutes immediately, hydro-thermal reaction is for 24 hours；Finally, being taken to reaction kettle cooling
The slurry of the zeolite containing synthetic product out, the mother liquor in filtering removal slurry, solid matter with deionized water be washed till after PH=6-8 in
120 DEG C of drying, then be placed in blowing air in 600 DEG C of muffle furnace and roast 6-8 hours, after the organic matter TPA in product is burnt out
Product is cooling, is exchanged 2 hours, totally 3 times with 0.5N hydrochloric acid, liquid-solid ratio 10 to 1,90 DEG C.After ion exchange, filtration washing is extremely
PH=3-5, drying, 550 DEG C of roasting 2h are to get zeolite (such as attached drawing) ru stick-like to length.It is collected in collector at this point, weighing
The weight of volatilizable ingredient water in reactant, the proportion for calculating the reactant in kettle at this time is Na2O:TPA2O:SiO2:Al2O3:
H20=1.5:1.0:400:1.0:12.
Example IV:
Firstly, by the default proportion Na of reactant2O:TPA2O:SiO2:Al2O3:H20=1.5:1.0:400:1.0:25 is weighed
The synthesis materials such as quantitative silicon raw material waterglass, aluminum feedstock aluminum sulfate, template TPAOH solution, sulfuric acid and deionized water carry out
Reactant is prepared；Then, prepared reactant is poured into reaction kettle, volume compactedness 80%, and the reaction kettle is heated
To 170 DEG C, this valve, hydro-thermal reaction 12h are turned off after opening high pressure valve release 8 minutes immediately；Finally, being taken to reaction kettle cooling
The slurry of the zeolite containing synthetic product out, the mother liquor in filtering removal slurry, solid matter with deionized water be washed till after PH=6-8 in
120 DEG C of drying, then be placed in blowing air in 600 DEG C of muffle furnace and roast 6-8 hours, after the organic matter TPA in product is burnt out
Product is cooling, is exchanged 2 hours, totally 3 times with 0.5N hydrochloric acid, liquid-solid ratio 10 to 1,90 DEG C.After ion exchange, filtration washing is extremely
PH=3-5, drying, 550 DEG C of roasting 2h are to get to cellular zeolite.It can in the reactant collected in collector at this point, weighing
The weight of volatile ingredient water, the proportion for calculating the reactant in kettle at this time is Na2O:TPA2O:SiO2:Al2O3:H20=1.5:
1.0:400:1.0:6。
The characterization of synthetic product:
The general analysis x-ray powder of diffracting spectrum (XRD) domestic production of crystalline product structure spreads out in the various embodiments described above
Penetrate instrument test, 5-35 ° of scanning range/2 θ.The winged desk type scanning electronic microscope of receiving of the pattern Holland production of crystalline product
(SEM) its photo is shot.
Catalytic property evaluation:
The zeolite molecular sieve number consecutively that will be prepared in four embodiments of the invention: A, B, C and D, and tablet press machine is used respectively
It is broken into particle again after being pressed into book piece, sub-sieve screens out fine powder and takes (about 6 grams or so) of 10 milliliters of 20-40 mesh particle to be used as catalyst
It is placed in fixed bed reactors and evaluates its catalytic performance.It is anti-that reactant methanol aqueous solution is input to reaction bed with electronic metering pump
It answers in device.480 DEG C of reaction temperature, the liquid hourly space velocity (LHSV) 1.0 of reactant input-1.Reaction product its each group of gas chromatograph for determination
At content, calculate the methanol conversion of catalyst, ethylene, propylene, the selectivity and catalyst of light olefin (C2+C3+C4)
The single trip use service life.The single trip use service life is defined as filling catalyst to be measured in fixed reactor from being pumped into methanol reactant
Termination reaction accumulative total reaction time (hour when starting to be carried out continuously catalysis reaction, be lower than 98% to methanol conversion-1).Tool
Body evaluation result see the table below 1.
The methanol dewatered light olefin catalytic property of zeolite in each embodiment of table 1
Above-mentioned number can be waved it was demonstrated that with proposed by the present invention during hydro-thermal reaction carries out by discharging in reactant
The method of the organic or inorganic component of hair can by the proportion of reactant, such as the present invention in H2O/SiO2, from what is matched substantially
25, be gradually respectively reduced to 19,12 and 6, under 170 DEG C of reaction temperature, the hydro-thermal reaction time from 48 hours, gradually divide
It does not foreshorten to 36,24 and 12 hours.The pattern of synthesized zeolite from square block, respectively become rice-shaped, length it is stick-like,
Honeycomb.With the change of zeolite product crystal morphology, made corresponding zeolite powder catalyst is converted into light olefin in methanol
Propylene Selectivity in catalysis reaction successively improves, and has been increased to 49.2%, P/E ratio by 44.2%, 45.5%, 48.7%
Successively 7.6 have been increased to from 4.9,5.2,6.6.More importantly the single trip use service life of catalyst also gradually from 650h,
720h, 850h have been increased to 950h.The zeolite that this explanation is synthesized by the method for the present invention can be constructed to practical industrial catalyst.
It should be noted that TPAOH solution contains a large amount of water due to the waterglass in synthesis material, can not be prepared with it
H2O/SiO2Reaction mixture lower than 15, with reaction unit proposed by the present invention, during hydro-thermal reaction carries out, by releasing
Put volatilizable organic or inorganic component in reactant method can by the proportion of reactant, such as the present invention in H2O/SiO2
6 are reduced to, synthetic reaction object at this time is equivalent to extremely dense system.Dense due to reactant, the hydro-thermal reaction time can also
It is obviously shortened, this can reduce energy consumption and improve the production efficiency of one-pot in industrial production.With important actual use valence
Value.
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by those skilled in the art
Mind and range.In this way, if these modifications and changes of the present invention belongs to the range of the claims in the present invention and its equivalent technologies
Within, then the present invention is also intended to include these modifications and variations.
Claims (10)
1. a kind of synthetic method of silica-rich zeolite molecular sieve, which comprises the steps of:
Reactant is prepared: suitable silicon source, silicon source, template, sulfuric acid and deionized water being taken to carry out pre- establishing according to default step
The reactant of ratio is prepared；
Zeolite product is produced: the reactant being placed in synthesizer and carries out hydro-thermal reaction, when temperature rises to preset water
When thermal response temperature, the volatilizable component of predetermined amount in reactant is discharged outward by the synthesizer, fill the synthesis
The proportion for setting middle reactant changes, to form the zeolite product of predetermined pattern；
Molecular sieve is produced: the slurry containing the zeolite product is taken out after the synthesizer is cooling, through filtering, washing, roasting
And ion-exchange treatment, obtain zeolite molecular sieve.
2. the synthetic method of silica-rich zeolite molecular sieve according to claim 1, which is characterized in that above-mentioned zeolite product is produced
In, the predetermined amount of the volatile component discharges the time of volatile material outward by the synthesizer to determine.
3. the synthetic method of silica-rich zeolite molecular sieve according to claim 1, which is characterized in that above-mentioned reactant is prepared
In, the silicon source is waterglass and/or silica solution, and source of aluminium is aluminum sulfate, the tetrapropylammonium hydroxide that the template is.
4. the synthetic method of silica-rich zeolite molecular sieve according to claim 1, which is characterized in that above-mentioned reactant is prepared
In, the default proportion of the reactant is Na2O:TPA2O:SiO2:Al2O3:H20=1.5:1.0:400:1.0:25.
5. the synthetic method of silica-rich zeolite molecular sieve according to claim 1, which is characterized in that above-mentioned zeolite product is produced
In, the temperature of the hydro-thermal reaction is 170 DEG C.
6. the synthetic method of silica-rich zeolite molecular sieve according to claim 1, which is characterized in that above-mentioned zeolite product is produced
In, the time of the hydro-thermal reaction is 12-48 hours.
7. the synthetic method of silica-rich zeolite molecular sieve according to claim 1, which is characterized in that the zeolite product it is pre-
Setting looks are square block, rice-shaped, thin stick-like or honeycomb.
8. a kind of synthesizer of silica-rich zeolite molecular sieve characterized by comprising
Reaction kettle；
Mechanism for opening/closing is arranged on the reaction kettle, opens when the temperature of reaction kettle rises to preset reaction temperature, simultaneously
Volatilizable component in the reaction mixture of release predetermined amount outward, so that the proportion of reactant changes in the reaction kettle
Become；
Cooling body is connected with the mechanism for opening/closing, for cooling down in reaction process through the mechanism for opening/closing from described anti-
The volatile material released in kettle is answered, in order to be collected to the volatile material after cooling；
Collector is connected with the cooling body, for collecting the volatile material cooling through the cooling body.
9. the synthesizer of silica-rich zeolite molecular sieve according to claim 5, which is characterized in that the mechanism for opening/closing packet
It includes:
It can pressure-releasing type high pressure valve for discharge volatizable material in the reaction kettle.
10. the synthesizer of silica-rich zeolite molecular sieve according to claim 5, which is characterized in that the cooling body packet
It includes:
Cooling coil for the cooling volatizable material released through the mechanism for opening/closing.
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